EP2530691A2 - Verfahren zur Herstellung einer Fotoelektrodenstruktur und sich daraus ergebende Fotoelektrodenstruktur - Google Patents

Verfahren zur Herstellung einer Fotoelektrodenstruktur und sich daraus ergebende Fotoelektrodenstruktur Download PDF

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Publication number
EP2530691A2
EP2530691A2 EP12162663A EP12162663A EP2530691A2 EP 2530691 A2 EP2530691 A2 EP 2530691A2 EP 12162663 A EP12162663 A EP 12162663A EP 12162663 A EP12162663 A EP 12162663A EP 2530691 A2 EP2530691 A2 EP 2530691A2
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EP
European Patent Office
Prior art keywords
oxide
light
scattering layer
nanowire
titanium
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EP12162663A
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English (en)
French (fr)
Inventor
Byong-Cheol Shin
Ji-Won Lee
Chang-Wook Kim
Do-Young Park
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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Priority to US13/481,670 priority Critical patent/US20120305067A1/en
Publication of EP2530691A2 publication Critical patent/EP2530691A2/de
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/209—Light trapping arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • One or more embodiments of the present invention relate to methods of forming a photoelectrode structure.
  • a dye-sensitized solar cell consists of a photoelectrode, an opposite electrode, and an electrolyte.
  • the photoelectrode is prepared by adsorbing metal oxide nanoparticles having a wide band gap energy and a photosensitive dye to a transparent substrate.
  • the opposite electrode is prepared by coating a transparent substrate with platinum.
  • the photosensitive dye absorbs solar light incident upon the cell and transitions the light to an excited state, thereby sending electrons to a conduction band of metal oxide. Conducted electrons move toward the photoelectrode and flow into an external circuit to deliver electric energy. The electrons (whose energy state is lowered by an amount corresponding to the delivered electric energy) move toward the opposite electrode. Then, the photosensitive dye is supplied with a number of electrons that is identical to the number of electrons that have moved to the metal oxide from the electrolyte solution, thus, reverting to the original state. In this regard, the electrolyte receives electrons from the opposite electrode due to a redox reaction, and delivers the electrons to the photosensitive dye.
  • the photoelectrode includes a light-absorbing layer containing metal oxide nanoparticles coated with dye, and a light-scattering layer that sends light that is not absorbed by the light-absorbing layer back to the light-absorbing layer. Since the light-scattering layer additionally scatters unabsorbed light, photoelectric conversion efficiency may be enhanced. However, the light-scattering layer generally contains metal oxide particles having a relatively large particle size of about 200 to about 500 nm, which particles only have light-scattering capability and do not deliver generated photoelectrons to a transparent conductive substrate.
  • a method of manufacturing a photoelectrode structure induces light scattering and provides a delivery pathway for generated photoelectrons so as to increase photocurrent density and enhance the adhesive strength of the light-scattering layer to the photoanode substrate.
  • a method of manufacturing a photoelectrode structure includes: disposing a light-scattering layer comprising a nanowire on a photoanode substrate; and applying an inorganic binder solution to the light-scattering layer to fix the light-scattering layer on the photoanode substrate.
  • FIG. 1 is a schematic cross-sectional view of a photoelectrode structure prepared according to an embodiment of the present invention
  • FIGS. 2 and 3 are scanning electron microscopy (SEM) images of a surface of a light-scattering layer of a dye-sensitized solar cell manufactured according to Example 1 taken at different magnifications;
  • FIG. 4 is a SEM image of a microstructure (a) of TiO 2 nanowires of a photoelectrode structure manufactured in Example 4 and a cross-section microstructure (b) of the photoelectrode structure;
  • FIG. 5 is a SEM image of a microstructure (a) of an interface of TiO 2 nanowires and a light-absorbing layer in the photoelectrode structure manufactured in Example 4 and a microstructure (b) of the interface when tilted;
  • FIG. 6 is a graph comparing the photocurrent and voltage of the dye-sensitized solar cells manufactured according to Example 1 and Comparative Examples 1 and 2;
  • FIG. 7 is a graph comparing the incident photon to current efficiencies (IPCE) of the dye-sensitized solar cells manufactured according to Example 1 and Comparative Examples 1 and 2.
  • a method of manufacturing a photoelectrode structure includes disposing a light-scattering layer including a nanowire on a photoanode substrate; and applying an inorganic binder solution to the light-scattering layer to fix the light-scattering layer on the photoanode substrate.
  • the photoanode substrate may include a light-transmissible conductive substrate, and a light-absorbing layer disposed on the light-transmissible conductive substrate, where the light-absorbing layer includes nanoparticles to which dye is absorbed.
  • the light-transmissible conductive substrate may be, for example, a transparent substrate coated with a conductive film.
  • the material for forming the conductive film may be indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), indium zinc oxide (IZO), aluminium doped zinc oxide (AZO), gallium doped zinc oxide (GZO), SnO 2 , In 2 O 3 , ZnO, and conductive impurity-doped TiO 2 .
  • the material for forming the conductive film may be any one of various transparent conductive oxides that are used in the art.
  • the conductive film may be formed by depositing at least one of these oxides, or a combination of oxides.
  • the transparent substrate that supports the conductive film of the light-transmissible conductive substrate may be transparent so as to allow external light to enter, and may be a transparent inorganic substrate formed of quartz or glass, or a plastic substrate. If a flexible dye-sensitized solar cell is desired, a plastic substrate may be suitable.
  • a plastic material for the substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polypropylene (PP), polyimide (PI), triacetyl cellulose (TAC), and polystyrene.
  • the light-absorbing layer disposed on the light-transmissible conductive substrate may include nanoparticles to which dye is absorbed.
  • An average particle size of the nanoparticles may be about 5 to about 50 nm. In some embodiments, for example, the average particle size of the nanoparticles may be about 5 to about 20 nm. In other embodiments, the average particle size of the nanoparticles may be about 10 to about 50 nm. If the average particle size of nanoparticles is within these ranges, the specific surface area of the nanoparticles is sufficiently large, enabling better adsorption of the dye molecules, yielding a stronger intensity of absorbed light.
  • the nanoparticles may be a semiconductor material having a lower conduction band energy than the lowest unoccupied molecular orbital (LUMO) of the dye.
  • the nanoparticles may include at least one semiconductor material selected from titanium (Ti) oxide, tin (Sn) oxide, niobium (Nb) oxide, zirconium (Zr) oxide, tungsten (W) oxide, vanadium (V) oxide, zinc (Zn) oxide, copper (Cu) oxide, iron (Fe) oxide, lead (Pb) oxide, bismuth (Bi) oxide, cadmium (Cd) oxide, tantalum (Ta) oxide, strontium (Sr) oxide, indium (In) oxide, iridium (Ir) oxide, lanthanum (La) oxide, molybdenum (Mo) oxide, magnesium (Mg) oxide, aluminum (Al) oxide, yttrium (Y) oxide, scandium (Sc) oxide, samarium (Sm) oxide, gallium (G
  • the nanoparticles may include titanium dioxide (TiO 2 ), zinc oxide (ZnO), tin dioxide (SnO 2 ), niobium oxide (Nb 2 O 5 ) tungsten trioxide (WO 3 ), or a mixture thereof.
  • the nanoparticles may include titanium dioxide (TiO 2 ), which has good photoelectron generation efficiency.
  • the nanoparticles are not limited to the above list and may be any one of various semiconductor materials that are used in the art.
  • the nanoparticles may be porous so as to widen the surface area to which the dye is adsorbed, thereby enhancing the electron generation efficiency of the dye that generates the photoelectrons.
  • the dye that is adsorbed to the nanoparticles is a material that is directly engaged in generating photoelectrons.
  • the dye may be a dye that absorbs light in the visible spectrum and has a high absorption coefficient.
  • the LUMO of the dye is higher than the conduction band energy of the semiconductor material of the nanoparticles.
  • suitable dyes for use in forming the photoelectrode structure include organometallic compounds, organic compounds, and quantum dot inorganic compounds, such as InP, or CdSe.
  • suitable dyes for use in forming the photoelectrode structure include organometallic compounds, organic compounds, and quantum dot inorganic compounds, such as InP, or CdSe.
  • the organometallic compound include compounds including metals, such as aluminum (Al), platinum (Pt), palladium (Pd), europium (Eu), lead (Pb), iridium (Ir), or ruthenium (Ru).
  • the dye may be ruthenium-based N3, N719, or black dye, but is not limited thereto, and the dye may be any one of various dyes that are sensitive to solar light and used in the art.
  • the thickness of the light-absorbing layer may be equal to or less than about 20 ⁇ m. In some embodiments, for example, the thickness of the light-absorbing layer is about 1 to about 20 ⁇ m. In other embodiments, the thickness of the light-absorbing layer is about 1 to about 15 ⁇ m.
  • the light-absorbing layer has high serial resistance due to its structure. Since the increase in serial resistance leads to a decrease in conversion efficiency, controlling the thickness of the light-absorbing layer within the ranges described above sustains the function of the light-absorbing layer while maintaining the serial resistance at low levels, thereby preventing decreases in conversion efficiency.
  • the photoanode substrate may be prepared using any method that is known in the art.
  • the photoanode substrate may be prepared by applying a paste composition including nanoparticles (for example, titanium dioxide nanoparticles), a binder, and a solvent to a light-transmissible conductive substrate by spin coating, dip coating, or the like to the desired thickness and then heat treating the resultant structure.
  • an adhesive force between the light-scattering layer and the photoanode substrate may be increased by simultaneously heat treating the nanoparticles that are applied to form the light-absorbing layer and the nanowires that are deposited thereon to form the light-scattering layer, so that at least a portion of the nanowires present at the interface with the light-absorbing layer is embedded in the light-absorbing layer.
  • thermal compression or a steaming treatment using an adhesive material such as tetrahydrofurane (THF) may be performed before heat treatment of the deposited nanowires.
  • the photoanode substrate may be a light-transmissible conductive substrate on which a light-absorbing layer is not disposed. If a separate light-absorbing layer is not disposed on the light-transmissible conductive substrate as described above, the dye may be adsorbed to the light-scattering layer. Alternatively, nanoparticles (which are used in the light-absorbing layer), may be further included in the light-scattering layer and dye is adsorbed to the nanoparticles, so as to provide a light absorbing function and a photoelectron generation function to the light-scattering layer.
  • a light-scattering layer including a nanowire is disposed on the photoanode substrate.
  • the nanowire included in the light-scattering layer may have conductivity and a one-dimensional linear structure.
  • the diameter of the nanowire may be controlled to about 100 to about 600 nm, for example, about 200 to about 500 nm.
  • the nanowire may include at least one semiconductor material selected from titanium (Ti) oxide, tin (Sn) oxide, niobium (Nb) oxide, zirconium (Zr) oxide, tungsten (W) oxide, vanadium (V) oxide, zinc (Zn) oxide, copper (Cu) oxide, iron (Fe) oxide, lead (Pb) oxide, bismuth (Bi) oxide, cadmium (Cd) oxide, tantalum (Ta) oxide, strontium (Sr) oxide, indium (In) oxide, iridium (Ir) oxide, lanthanum (La) oxide, molybdenum (Mo) oxide, magnesium (Mg) oxide, aluminum (Al) oxide, yttrium (Y) oxide, scandium (Sc) oxide, samarium (Sm) oxide, gallium (Ga) oxide, strontium titanium (SrTi) oxide, potassium tantalum (KTa) oxide, barium titanium (BaTi) oxide, iron titanium (F
  • the nanowire may be a titanium dioxide (TiO 2 ) nanowire, a zinc oxide (ZnO) nanowire, or a mixture thereof.
  • TiO 2 titanium dioxide
  • ZnO zinc oxide
  • the nanowire is not limited to these materials, and may include any one of various semiconductor materials that have light-scattering effect and conductivity and that are used in the art.
  • the nanowire and the nanoparticles may be formed using identical or different semiconductor materials.
  • the nanowire may be formed in various ways, for example, chemical vapor deposition (CVD), laser ablation, thermal evaporation, electrodeposition, or electrospinning, etc.
  • the nanowire may be formed by electrospinning. Due to the electrospinning, the light-scattering layer may have a structure in which the nanowire is tangled.
  • disposing the light-scattering layer may include electrospinning a precursor solution including a nanowire precursor on a surface of the photoanode substrate and then heat treating the precursor solution.
  • the precursor solution may be prepared by adding a nanowire precursor to a solvent, and if necessary, the solution may further include a binder, an acid for controlling pH, or other additives.
  • the nanowire precursor may include, for example, at least one selected from titanium isopropoxide, titanium ethoxide, titanium chloride, and titanium methoxide. If a titanium compound is used as the nanowire precursor as described above, a light-scattering layer including a titanium dioxide nanowire may be formed. However, the nanowire precursor is not limited thereto and may be any one of various precursors that form titanium dioxide by heat treatment.
  • the amount of the nanowire precursor may be about 5 to about 30 weight (wt.)% based on a total weight of the nanowire precursor and the solvent. In some embodiments, for example, the amount of the nanowire precursor may be about 10 to about 20 wt.% based on the total weight of the nanowire precursor and the solvent. If the amount of the nanowire precursor is within these ranges, the nanowire precursor may be uniformly dispersed in the precursor solution and thus a uniform nanowire may be formed.
  • Nonlimiting examples of the solvent for dissolving the nanowire precursor including terpineol, ethanol, distilled water, ethylene glycol, alpha-terpineol and the like.
  • the solvent may be any solvent that is used in the art.
  • An amount of the solvent may be about 70 to about 95 wt.% based on the total weight of the nanowire precursor and the solvent. In some embodiments, for example, the amount of the solvent may be about 80 to about 90 wt.% based on the total weight of the nanowire precursor and the solvent. If the amount of the solvent is within these ranges, the nanowire precursor may be uniformly dispersed in the precursor solution.
  • the precursor solution may further include a binder for binding the nanowire (which is formed by electrospinning the precursor solution) to the photoanode substrate with a desired level of adhesive strength.
  • a binder for binding the nanowire (which is formed by electrospinning the precursor solution) to the photoanode substrate with a desired level of adhesive strength.
  • the binder include polyvinyl pyrrolidone (PVP), ethyl cellulose, and hydroxypropyl cellulose.
  • the binder may be any one of various binders that are used in the art and that are thermally decomposed at a temperature of 400°C or higher.
  • An amount of the binder in the precursor solution may be about 10 to about 40 parts by weight based on 100 parts by weight of the nanowire precursor. In some embodiments, for example, the amount of the binder in the precursor solution may be about 20 to about 30 parts by weight based on 100 parts by weight of the nanowire precursor. If the amount of the binder is within these ranges, the precursor solution may retain an appropriate viscosity and thus, electrospinning may be easily performed, and the formed nanowires may have an appropriate binding force.
  • the precursor solution may further include an acid for controlling the degree of acidity (pH).
  • the precursor solution may include an acetic acid.
  • the precursor solution may further include other additives.
  • the precursor solution is electrospun on a surface of the photoanode substrate and then heat treated to form a light-scattering layer.
  • the precursor solution may be electrospun to form the light-scattering layer such that the light-scattering layer covers at least a portion of the light-absorbing layer disposed on the light-transmissible conductive substrate, and such that at least a portion of the light-scattering layer contacts the light-transmissible conductive substrate.
  • the light-scattering layer including a nanowire contacts the light-transmissible conductive substrate
  • the light-scattering layer may induce light scattering and may also provide a delivery pathway for transporting photoelectrons generated by the light-absorbing layer to the light-transmissible conductive substrate through the nanowire of the light-scattering layer.
  • the number of interfaces through which photoelectrons pass is relatively decreased. Accordingly, losses of photoelectrons due to their recombination may be reduced, and photocurrent density may be increased, thus increasing photoelectric conversion efficiency.
  • the electrospinning may be performed, for example, at a speed of about 10 to about 20 ⁇ l/min for about 10 to about 30 minutes with the precursor solution at a voltage of about 5 to about 10 kV. Under these electrospinning conditions, the thickness of the light-scattering layer may be controlled according to the electrospinning time.
  • a hot plate may be used to maintain the temperature of the photoanode substrate at about 100 to about 350°C.
  • the adhesive strength of the electrospun nanowire may be increased.
  • heat treatment of the resultant structure may be performed at a temperature of about 400 to about 600°C.
  • the heat treatment temperature may be about 400 to about 550°C, and in some embodiments, for example, about 400 to about 500°C. If the heat treatment temperature is too high, the photoanode substrate may be bent. On the other hand, if the heat treatment temperature is too low, it is difficult to calcinate titanium dioxide. Accordingly, if the heat treatment temperature is within the ranges described above, the light-scattering layer may have fewer defects and high photoconductive efficiency.
  • a thickness of the light-scattering layer may be about 0.1 to about 10 ⁇ m. In some embodiments, for example, the thickness of the light-scattering layer may be about 0.5 to about 3 ⁇ m. If the thickness of the light-scattering layer is within these ranges, the light-scattering layer may have high photoconductivity efficiency and good light-scattering effect.
  • the dye may be adsorbed to the light-scattering layer. If the dye is adsorbed to the nanowire of the light-scattering layer, the light-scattering layer may absorb solar light and generate photoelectrons, thereby performing (in addition to its original light scattering function) a function of generating and transporting photoelectrons.
  • the dye used herein may be identical to the dye that is described above for the light-absorbing layer. Also, selectively, adsorbing the dye to the light-scattering layer may be performed after the light-scattering layer is fixed on the photoanode substrate by coating with an inorganic binder solution.
  • the inorganic binder solution is disposed on the light-scattering layer to fix the light-scattering layer on the photoanode substrate.
  • the nanowire of the light-scattering layer (obtained by heat treating the nanowire precursor solution after electrospinning) may have a certain level of adhesive strength, the adhesive strength of the nanowire may not be sufficiently strong to completely fix the light-scattering layer on the photoanode substrate. Accordingly, by coating the light-scattering layer with the inorganic binder solution, the adhesive strength may be enhanced and the light-scattering layer may be fixed on the photoanode substrate.
  • Applying the inorganic binder solution may be performed by at least one of spin coating, dip coating, roll coating, screen coating, spray coating, and screen printing.
  • the method may further include, after applying the inorganic binder solution, heat treating the light-scattering layer coated with the inorganic binder solution.
  • the light-scattering layer coated with the inorganic binder solution may be heat treated at a temperature of about 250 to about 500°C.
  • the solvent or binder included in the inorganic binder solution may thermally decompose, and the inorganic material included in the inorganic binder solution may be attached to a surface of the nanowire, or coated on a surface of the nanowire, thereby fixing the light-scattering layer on the photoanode substrate with enhanced adhesive force between nanowires.
  • the coating and heat treatment of the inorganic binder solution may be repeatedly performed as needed.
  • the inorganic binder solution may be a TiO 2 sol.
  • the TiO 2 sol may include TiO 2 nanoparticles having a particle diameter of about 5 to about 50 nm.
  • the TiO 2 sol may be a sol in which TiO 2 nanoparticles are dispersed in a binder (such as ethylcellulose, hydroxypropylcellulose, etc.) by using a phosphate ester-based surfactant or a polar acidic ester of a long chain alcohol-based additive as a dispersing agent for dispersing the TiO 2 nanoparticles.
  • a binder such as ethylcellulose, hydroxypropylcellulose, etc.
  • the TiO 2 nanoparticles remain attached to the nanowire through heat treatment after application, and improve the adhesive strength between nanowires.
  • the TiO 2 nanoparticles attached to the surface of the nanowire provide a light absorbance function or a light scattering function.
  • the inorganic binder solution may be an NbCl 5 -containing solution.
  • the NbCl 5 -containing solution may include about 10 to about 40 mM of NbCl 5 .
  • the NbCl 5 -containing solution may include a solvent such as ethanol, distilled water, ethylene glycol, terpineol, alpha-terpineol, or the like.
  • the NbCl 5 -containing solution may further include other additives as desired.
  • the solvent is removed and NbCl 5 is converted into an Nb 2 O 5 oxide which remains coated on the surface of the nanowire.
  • the Nb 2 O 5 oxide coated on the surface of the nanowire may enhance the binding force of the nanowire and prevent the recombination of photoelectrons that may occur in the light-scattering layer, thereby improving photocurrent density.
  • a photoelectrode structure includes: a photoanode substrate; and a light-scattering layer disposed on the photoanode substrate and including a nanowire, wherein the light-scattering layer is fixed on the photoanode substrate by an inorganic binder.
  • FIG. 1 is a schematic cross-sectional view of a photoelectrode structure 1 prepared according to an embodiment of the present invention.
  • the photoelectrode structure 1 includes a photoanode substrate 10 and a light-scattering layer 20, and the photoanode substrate 10 may include a light-transmissible conductive substrate 11 and a light-absorbing layer 12 that is disposed on the light-transmissible conductive substrate 11 and that includes nanoparticles to which a dye is adsorbed.
  • the light-scattering layer 20 may be formed as a nanowire tangled structure by electro-spinning.
  • the light-scattering layer 20 may be disposed such that the light-scattering layer 20 covers at least a portion of the light-absorbing layer 12 and at least a portion of the light-scattering layer 20 contacts the light-transmissible conductive substrate 11. By doing this, electrons formed in the light-absorbing layer 12 may be easily delivered to the light-transmissible conductive substrate 11.
  • photoelectrons move through the nanoparticle interfaces of the light-absorbing layer 12 to the light-transmissible conductive substrate 11, and also move through the nanowire of the light-scattering layer 20 to the light-transmissible conductive substrate 11. Due to the additional pathway for delivering photoelectrons, the number of interfaces through which photoelectrons pass may be relatively reduced, the loss caused by recombination of photoelectrons may be reduced, and photocurrent density may be increased.
  • the light-scattering layer 20 may be fixed on the photoanode substrate 10 by an inorganic binder.
  • an organic binder solution may be applied on the light-scattering layer 20, followed by heat treating, thereby fixing the light-scattering layer 20 on the photoanode substrate 10.
  • the inorganic binder solution may be TiO 2 sol, and the TiO 2 sol may include TiO 2 nanoparticles. When the TiO 2 sol is used, TiO 2 nanoparticles of the inorganic binder solution may remain as being attached to the nanowire through the heat treatment so that a binding force of the nanowire may be increased.
  • the TiO 2 nanoparticles of the inorganic binder attached to the nanowire surface may function as light absorption and light scattering simultaneously.
  • a particle diameter of the TiO 2 nanoparticles may be in a range of about 5 to about 50 nm.
  • the inorganic binder solution may be an NbCl 5 -containing solution.
  • the NbCl 5 -containing solution may include about 10 to about 40 mM concentration of NbCl 5 .
  • a solvent may be removed and NbCl 5 is changed into Nb 2 O 5 oxide, thereby remaining coated on the surface of the nanowire.
  • the Nb 2 O 5 oxide coated on the surface of the nanowire may increase a binding force of the nanowire and may also prevent recombination of photo electrons that may occur in the light-scattering layer 20 to increase a photocurrent density.
  • At least a portion of the nanowire of the light-scattering layer 20 present at the interface with the light-absorbing layer 12 may be embedded in the light-absorbing layer 12.
  • a dye-sensitized solar cell including a photoelectrode structure prepared as described above may have enhanced photoelectric conversion efficiency.
  • a dye-sensitized solar cell includes the photoelectrode structure described above; a second electrode facing the light-transmissible conductive substrate (the light-transmissible conductive substrate is hereinafter referred to as the 'first electrode'); and an electrolyte between the light-transmissible conductive substrate (that is, the first electrode) and the second electrode.
  • the photoelectrode structure is the same as described above.
  • the second electrode may face the first electrode of the photoelectrode structure, and the electrolyte may be disposed between the first electrode of the photoelectrode structure and the second electrode.
  • the second electrode and the electrolyte may have conventional structures, and may be manufactured using conventional manufacturing processes.
  • a material for forming the second electrode may be any conductive material.
  • a conductive layer may be formed on a side of the second electrode facing the first electrode.
  • the second electrode may include: a transparent substrate; and a transparent electrode including a transparent conductive oxide and a catalyst for activating a redox couple, which are disposed on the transparent substrate.
  • the transparent substrate used in the second electrode may support the transparent electrode and the catalyst, and may be a transparent inorganic substrate formed of, for example, quartz or glass, or may be a plastic substrate.
  • the transparent electrode may include a transparent conductive oxide, and as described above with respect to the first electrode (that is, the light-transmissible conductive substrate), the transparent conductive oxide may be any one of various transparent conductive oxides that are used in the art.
  • the transparent conductive oxide include indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), indium zinc oxide (IZO), aluminium doped zinc oxide (AZO), gallium doped zinc oxide (GZO), SnO 2 , In 2 O 3 , ZnO, and conductive impurity-doped TiO 2 .
  • the transparent electrode may be formed by depositing at least one of these oxides, or a combination of the oxides.
  • the catalyst activates a redox couple, and may include platinum, gold, silver, ruthenium, palladium, iridium, rhodium (Rh), osmium (Os), carbon (C), WO 3 , TiO 2 , or a conductive material, such as a conductive polymer.
  • the electrolyte may be disposed between the first electrode and the second electrode, and receives electrons from the second electrode due to a redox reaction and delivers the electrons to the dye.
  • the electrolyte may include a redox couple, such as I - /I 3 - .
  • the source for the I - ion may be Lil, Nal, alkylammonium iodine or imidazolium iodine, and the I 3 - ion may be generated by dissolving I 2 in a solvent.
  • the medium for the electrolyte may be a liquid such as acetonitrile or a polymer such as polyethyleneoxide.
  • a liquid medium include carbonates, nitrile compounds, and alcohols.
  • the liquid medium may be propylene carbonate, acetonitrile, or methoxy acetonitrile.
  • Nonlimiting examples of a polymer medium include polyacrylonitriles (PAN), acryl-ionic liquid combinations, pyridines, and polyethyleneoxides (PEO). Also, a gelator may be added to the liquid electrolyte to prepare a gel-type electrolyte.
  • PAN polyacrylonitriles
  • PEO polyethyleneoxides
  • a gelator may be added to the liquid electrolyte to prepare a gel-type electrolyte.
  • a titanium dioxide nanoparticle paste (PST 18NR, manufactured by JGC C&C Company) was sequentially coated, dried, coated, and dried on a conductive thin film formed of FTO (2.8T, T: Glass thickness) as a light-transmissible conductive substrate (first electrode).
  • the formed titanium dioxide film was heat treated at a temperature of 500°C for about 30 minutes, and then sequentially coated, dried, coated, dried, and heat treated, thereby forming a light-absorbing layer having a thickness of 10 ⁇ m.
  • titanium isopropoxide 1.5 g of titanium isopropoxide, 0.604 ml (0.634 g) of acetic acid, and 3 ml (2.367 g) of ethanol were mixed to prepare a mixture.
  • the titanium dioxide nanowire precursor solution was electrospun on the light-absorbing layer at a voltage of 10 kV at a rate of 15 ⁇ l/min for 30 minutes.
  • the spray nozzle used had an inner diameter of 1 mm, and a distance between the spray nozzle and the light-absorbing layer was 30 cm.
  • the first electrode on which the light-absorbing layer was disposed was maintained at a temperature of 300°C using a hot plate.
  • the resultant structure was heat treated at a temperature of 500°C for 30 minutes, thereby forming a light-scattering layer having a thickness of 2 ⁇ m.
  • FIGs. 2 and 3 are scanning electron microscopy (SEM) images of the surface of the light-scattering layer of the dye-sensitized solar cell manufactured according to Example 1.
  • SEM scanning electron microscopy
  • the resultant structure was maintained at a temperature of 80°C and then immersed in a dye dispersion solution in which N719 as the dye was dissolved at a concentration of 0.3 mM in ethanol, and a dye adsorption treatment was performed thereon for 24 hours. Then, the dye-adsorbed light-absorbing layer was washed with ethanol and dried at room temperature.
  • a Pt layer was deposited on a fluorine-doped tin oxide transparent conductor as an opposite electrode by sputtering, and then a micropore was formed therein for electrolyte injection using a drill having a diameter of 0.6 mm.
  • thermoplastic polymer film having a thickness of 60 ⁇ m was disposed between the photoelectrode structure and the opposite electrode and compressed at a temperature of 90°C for 10 seconds, thereby combining the two electrodes.
  • a redox electrolyte was injected through the micro pore formed in the opposite electrode, and then the micro pore was sealed using a cover glass and a thermoplastic polymer film, thereby completing the manufacture of a dye-sensitized solar cell.
  • the redox electrolyte was prepared by dissolving 0.62 M 1-butyl-3-methylimidazolium iodide, 0.1 M Lil, 0.5 M I 2 , and 0.5M 4-tert-butylpyridine in an acetonitrile.
  • a dye-sensitized solar cell was manufactured as in Example 1, except that the temperature of the hot plate was maintained at 200°C during electrospinning when forming the light-scattering layer.
  • a dye-sensitized solar cell was manufactured as in Example 1, except that the temperature of the hot plate was maintained at 100°C during electrospinning when forming the light-scattering layer.
  • the dye-sensitized solar cells manufactured according to Examples 1 to 3 in which the temperature of the hot plate was respectively maintained at 300°C (Example 1), 200°C (Example 2) and 100°C (Example 3) when the nanowire precursor solution was electrospun were compared to each other. As a result, it was confirmed that the higher the temperature of the hot plate, the stronger the cohesive force of the formed light-scattering layer.
  • a dye-sensitized solar cell was manufactured as in Example 1, except that the TiO 2 nanoparticle paste coated and dried on the FTO glass was not heat treated and the TiO 2 nanoparticle paste and subsequently electro-spun TiO 2 nanowire were simultaneously calcined at the temperature of 500°C for about 30 minutes.
  • FIG. 4 is a SEM image of a microstructure (a) of a TiO 2 nanowire surface of the photoelectrode structure manufactured according to Example 4 and a cross-section microstructure (b) of the photoanode substrate.
  • the image shown in FIG. 4 is an image enlarged at a magnification of 5,000 and a unit length in this case was 5 ⁇ m.
  • FIG. 5 is a SEM image of a microstructure (a) of an interface of the TiO 2 nanowire and the light-absorbing layer and a microstructure (b) of the interface when tilted, which is observed at a magnification of 5,000. Referring to FIG. 5 , it was confirmed that the TiO 2 nanowire was embedded in the nanoparticles layer (light-absorbing layer) by simultaneous calcination and sintering.
  • a dye-sensitized solar cell was manufactured as in Example 1, except that a photoelectrode structure was used in which only a light-absorbing layer was formed on the light-transmissible conductive substrate (first electrode) without formation of the light-scattering layer.
  • a dye-sensitized solar cell was manufactured as in Example 1, except that a photoelectrode structure was used in which dye was adsorbed to the light-scattering layer and the dye-adsorbed light-scattering layer was not treated with an NbCl 5 0.1 M solution.
  • a xenon lamp was used as a light source, the solar conditions of the xenon lamp were adjusted using a standard solar cell (Fraunhofer Institute Solare Engeriessysysteme, Certificate No. C-ISE369, Type of material: Mono-Si+KG filter), and the power density used was 100 mW/cm 2 .
  • J is the value of the Y axis of the energy conversion efficiency curve
  • V is the value of the X axis of the energy conversion efficiency curve
  • Jsc and Voc are respectively the intercept values of the respective axes.
  • the dye-sensitized solar cell of Example 1 has higher photocurrent density than the dye-sensitized solar cells of Comparative Examples 1 and 2.
  • the increase in the photocurrent density may result from a decrease in solar light loss. This result may also be confirmed in Table 1.
  • the dye-sensitized solar cell of Example 1 has higher efficiency than the dye-sensitized solar cells of Comparative Examples 1 and 2.
  • IPCE Incident photon-to-current efficiencies
  • the dye-sensitized solar cell of Example 1 has a higher scattering effect than the dye-sensitized solar cell of Comparative Example 1, and has a similar scattering effect to that of the dye-sensitized solar cell of Comparative Example 2 (which was not doped with the NbCl 5 inorganic binder solution).
  • a method of forming a photoelectrode structure includes forming a light-scattering layer including a nanowire on a photoanode substrate to induce light-scattering and provide a delivery pathway for the generated photoelectrons, thereby increasing the photocurrent density and efficiency of the dye-sensitized solar cell. Also, an inorganic binder solution is applied to the light-scattering layer to enhance the adhesive force of the light-scattering layer to the photoanode substrate, thereby increasing the durability of the photoelectrode structure.

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JP2014124646A (ja) * 2012-12-25 2014-07-07 Disco Abrasive Syst Ltd レーザ加工方法および微粒子層形成剤
KR101472661B1 (ko) * 2013-02-25 2014-12-15 경북대학교 산학협력단 태양광 충방전 복합산화물 반도체 제조 및 이를 활용한 야간 수처리
WO2015054656A1 (en) * 2013-10-10 2015-04-16 California Institute Of Technology Protecting the surface of a light absorber in a photoanode
KR101710421B1 (ko) * 2015-09-25 2017-03-13 제주대학교 산학협력단 산화구리 나노막대/산화아연 나노가지로 구성된 광전극과 그 형성방법
CN107785173A (zh) * 2016-08-30 2018-03-09 东北师范大学 一种适用于弱光条件下量子点敏化太阳能电池的对电极材料及其制备方法
CN106971852A (zh) * 2017-04-14 2017-07-21 上海为然环保科技有限公司 一种改进型光阳极结构的染料敏化太阳能电池
CN107026023A (zh) * 2017-04-14 2017-08-08 上海耐相智能科技有限公司 基于太阳能蓄能的交通指示装置
CN106945837A (zh) * 2017-04-14 2017-07-14 上海博历机械科技有限公司 一种利用高效染料敏化太阳能电池的驱鸟无人机
CN108447692A (zh) * 2018-02-09 2018-08-24 深圳源广安智能科技有限公司 一种改进的光阳极以及染料敏化太阳能电池
CN108506869A (zh) * 2018-04-02 2018-09-07 深圳万智联合科技有限公司 一种光伏发电物联网led灯
CN108528536A (zh) * 2018-04-02 2018-09-14 深圳汇通智能化科技有限公司 一种对天然气瓶有隔热保护的太阳能光伏电池板客车顶棚
CN112301549B (zh) * 2020-10-20 2022-08-23 西安工程大学 一种静电纺金属纤维-铜复合高温导电膜层及其制备方法
KR102638485B1 (ko) * 2022-02-25 2024-02-20 성균관대학교산학협력단 태양광 흡수용 산화물 반도체의 제조 방법

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